Substituted 1,4 diaminobenzene compounds and oxidation dye precursor compositions containing same

ABSTRACT

New substituted 2,5-diamino-1-aminomethylbenzene compounds of formula (I), or physiologically compatible water-soluble salts thereof,                    
     are described as well as methods for preparing them. In addition, oxidation dye precursor compositions for dyeing keratin fibers, especially human hair, which each contain from 0.005 to 20 percent by weight of at least one of the new substituted 2,5-diamino-1-aminomethylbenzene compounds of formula (I), or their physiologically compatible water-soluble salts, are described. Methods for dyeing hair with ready-to-apply dye mixtures made by mixing these oxidation dye precursor compositions with an oxidizing agent, such as hydrogen peroxide solution, are also described.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to new substituted2,5-diamino-1-aminomethylbenzene compounds and oxidation dye precursorcompositions for dyeing keratin fibers, especially human hair,containing these compounds.

2. Prior Art

Oxidation dyes have been important in the field of dyeing keratinfibers, especially human hair, for a long time. Dyeing occurs byreaction of certain developer substances alone or with certain couplersubstances in the presence of a suitable oxidizing agent. It is knownfrom DE-PS 47349 that keratin fibers can be dyed in bright blond tobluish-black color tones by p-phenylenediamine according to theoxidizing agent used. Blue color tones are produced however by acombination of p-phenylenediamine and its derivative compounds withcertain coupler substances. Since only compounds that havespecifications or properties that, on the one hand, protect the usersufficiently and, on the other hand, produce a stable resistant colorthat lasts for a sufficient time can be employed, the selection ofsuitable developer and coupler substances is limited.

SUMMARY OF THE INVENTION

It has now been surprisingly found that certain p-phenylenediaminederivative compounds permit dyeing of keratin fibers, especially humanhair, an intense blue color, even without addition of a couplersubstance.

Thus intense colors, which are extraordinarily light-fast and wash-fast,are obtained when these p-phenylenediamine derivative compounds are usedin an oxidizing medium

According to the present invention these p-phenylenediamine derivativecompounds are substituted 2,5-diamino-1-aminomethylbenzene compounds offormula (I), or their physiologically compatible water-soluble salts,

wherein

R1, R2, R3, R4, R5, R6 and R7, independently of each other, eachrepresent H, a C₁- to C₆-alkyl group, a C₁- to C₄-hydroxyalkyl group, aC₂- to C₄-dihydroxyalkyl group or a C₁- to C₄-alkoxy-(C₁- to C₂-)alkylgroup or R1 and R2 and/or R3 and R4 and/or R5 and R6 together with the Natom form a four-member to eight-member aliphatic ring, with the provisothat at least two of the groups R1 to R6 each represent hydrogen;

R8 represents hydrogen, a halogen atom, a C₁- to C₄-alkyl group, a C₁-to C₄-hydroxyalkyl group or a C₁- to C₄-alkoxy group;

R9 represents a hydrogen, a halogen atom, a cyano group, a hydroxygroup, a C₁- to C₄-alkoxy group, a C₁- to C₄-hydroxyalkoxy group, a C₁-to C₆-alkyl group, a C₁- to C₄-alkylthioether group; a mercapto group;an amino group, a C₁- to C₄-alkylamino group, a C₁- toC₄-hydroxyalkylamino group, a di(C₁- to C₄-alkyl)amino group, a di(C₁-to C₄-hydroxyalkyl)amino group, a {dihydroxy(C₂- to C₄)-alkyl}aminogroup, a (C₁- to C₄-hydroxyalkyl)-C₁-C₄-alkylamino group, atrifluoromethane group, a C₁-C₄-hydroxyalkyl group or a C₃-C₄dihydroxyalkyl group; and

R10 represents hydrogen or a C₁- to C₆-alkyl group.

For example, the following compounds of formula (I) can be named asexamples: 2-((2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-aminophenylamino)methyl)-1,4-diaminobenzene;2-((3-bis(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene;2-((3-dimethylaminophenylamino)-methyl)-1,4-diaminobenzene;2-((4-amino-phenylamino)methyl)-1,4-diaminobenzene;2-((4-bis-(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene;2-((4-dimethylamino-phenylamino)methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((2-aminophenylamino)methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((2-bis(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis-(hydroxyethyl)-2-((2-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((3-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((3-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((4-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((2-amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((2-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((2-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((3-bis-(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((3-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((4-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-hydroxyethyl-2-((2-aminophenylamino)-methyl)-1,4-diaminobenzene;N¹-hydroxyethyl-2-((2-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-hydroxyethyl-2-((2-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-hydroxyethyl-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-hydroxyethyl-2-((3-bis(hydroxyethyl)amino-phenylamino)methyl)1,4-diaminobenzene;N¹-hydroxyethyl-2-((3-dimethylamino-phenylamino)methyl)-1,4-diaminobenzene;N¹-hydroxyethyl-2-((4-aminophenylamino)-methyl)-1,4-diaminobenzene;N¹-hydroxyethyl-2-((4-bis(hydroxyethyl)-aminophenylamino)-methyl)-1,4-diaminobenzene;N¹-hydroxyethyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((2-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis-(hydroxyethyl)-2-((2-bis(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((2-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((3-aminophenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((3-bis(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((3-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis-(hydroxyethyl)-2-((4-bis(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((2-aminophenylamino)-methyl)-1,4-diaminobenzene,N⁴-dihydroxypropyl-2-((2-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((2-dimethylamino-phenylamino)methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((3-bis-(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((3-dimethylaminophenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((4-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((4-dimethylaminophenylamino)-methyl)-1,4-diaminobenzene;N⁴-hydroxyethyl-2-((2-aminophenylamino)methyl)-1,4-diaminobenzene,N⁴-hydroxyethyl-2-((2-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-hydroxyethyl-2-((2-dimethylamino-phenylamino)-methy)-1,4-diaminobenzene;N⁴-hydroxyethyl-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene-N⁴-hydroxyethyl-2-((3-bis(hydroxy-ethyl)amino-phenylamino)methyl)-1,4-diaminobenzene;N⁴-hydroxyethyl-2-((3-dimethylaminophenylamino)methyl)-1,4-diaminobenzene;N⁴-hydroxyethyl-2-((4-aminophenylamino)-methyl)-1,4-diaminobenzene;N⁴-hydroxyethyl-2-((4-aminophenylamino)-methyl)-1,4-diaminobenzene;N⁴-hydroxyethyl-2-((4-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-hydroxyethyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(dihydroxypropyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-hydroxyethylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(dihydroxypropyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-hydroxyethylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(dihydroxypropyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-hydroxyethylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-methylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((methyl-(2-(dihydroxypropylamino)-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((methyl-(2-amino-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((methyl-(2-bis(hydroxyethyl)amino-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((methyl-(3-(dihydroxypropylamino)-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((methyl-(3-amino-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((methyl-(3-bis(hydroxyethyl)amino-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((methyl-(4-(dihydroxypropylamino)-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((methyl-(4-amino-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((methyl-(4-bis(hydroxyethyl)amino-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((1-(2-amino-phenyl)-amino)-ethyl)-1,4-diaminobenzene;2-((1-(2-bis(hydroxyethyl)amino-phenyl)-amino)-ethyl)-1,4-diaminobenzene;2-((1-(2-dimethylamino-phenyl)-amino)-ethyl)-1,4-diaminobenzene;2-((1-(3-aminophenyl)-amino)-ethyl)-1,4-diaminobenzene;2-((1-(3-bis(hydroxyethyl)amino-phenyl)-amino)-ethyl)-1,4-diaminobenzene;2-((1-(3-dimethylamino-phenyl)-amino)-ethyl)-1,4-diaminobenzene;2-((1-(4-amino-phenyl)-amino)-ethyl)-1,4-diaminobenzene;2-((1-(4-bis-(hydroxyethyl)amino-phenyl)-amino)-ethyl)-1,4-diaminobenzene;2-((1-(4-dimethylamino-phenyl)-amino)-ethyl)-1,4-diaminobenzene;2-((2-((2,3-diamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-((2,4-diamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-((3,4-diamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((methyl-(2,3-diamino-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((methyl-(2,4-diamino-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-((methyl-(3,4-diamino-phenyl)-amino)-methyl)-1,4-diaminobenzene;2-(1-(2,3-diamino-phenylamino)-ethyl)-1,4-diaminobenzene;2-(1-(2,4-diamino-phenylamino)-ethyl)-1,4-diaminobenzene;2-(1-(3,4-diamino-phenylamino)-ethyl)-1,4-diaminobenzene;2-((2-(2-hydroxyethoxy)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(2-hydroxyethyl)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-chloro-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-hydroxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methoxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methyl-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(2-hydroxyethoxy)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(2-hydroxyethyl)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-chloro-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-hydroxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methoxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methyl-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-chloro-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-hydroxy-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methyl-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-chloro-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-hydroxy-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-methyl-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-chloro-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-hydroxy-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-methyl-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((6-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((6-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((6-chloro-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((6-hydroxy-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((6-methyl-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(2-hydroxyethoxy)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(2-hydroxyethyl)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-chloro-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-hydroxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-(3-methoxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methyl-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethoxy)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethyl)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-chloro-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-hydroxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-methoxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-methyl-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-(2-hydroxyethoxy)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-(2-hydroxyethyl)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-chloro-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-hydroxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-methoxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((5-methyl-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((6-(2-hydroxyethoxy)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((6-(2-hydroxyethyl)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((6-chloro-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((6-hydroxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((6-methoxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene2-((6-methyl -2-amino-phenylamino)-methyl)-1,4-diaminobenzene.

Compounds of formula (I) are preferred, in which (i) R₁, R₂, R₂ and R₄are each hydrogen and/or (ii) one or more of the groups R₅ to R₁₀ areeach hydrogen and/or (iii) R₅ and R₆, independently of each other, arehydrogen, a methyl group or a C₁- to C₄-hydroxyalkyl group or (iv) R₇,R₈, R₉ and R₁₀ are each hydrogen and R₅ and R₆ are, independently ofeach other, hydrogen, a C₁- to C₄-alkyl group, a C₁- to C₄-hydroxyalkylgroup or a C₂- to C₄-dihydroxyalkyl group or R₅ and R₆ together with theN atom form a four-member ring.

The following compounds of formula (I) are particularly preferred:2-((2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-aminophenylamino)-methyl)-1,4-diaminobenzene;2-((4-amino-phenylamino)methyl)-1,4-diaminobenzene;2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-dimethylamino-phenylamino)methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((3-aminophenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((4-bis(2-hydroxyethyl)amino-phenylamino)methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxy-ethyl)-2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-dihydroxypropylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-dihydroxypropylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-dihydroxypropylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-methylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(2-hydroxyethyl)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(2-hydroxyethyl)-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-chloro-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-chloro-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methoxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methoxy-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methyl-4-aminophenylamino)-methyl)-1,4-diaminobenzene;2-((2-methyl-4-bis(2-hydroxy-ethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(2-hydroxyethyl)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(2-hydroxyethyl)-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-chloro-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-chloro-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methoxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methoxy-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methyl-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methyl-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethoxy)-3-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzeneand2-((4-(2-hydroxyethyl)-3-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene.

The compounds of formula (I) can be used both as free bases and also inthe form of their physiologically compatible salts with inorganic ororganic acids, for example with hydrochloric acid, sulfuric acid,phosphoric acid, acetic acid, propionic acid, lactic acid or citricacid.

The manufacture of the substituted 2,5-diamino-1-aminomethylbenzenecompounds of formula (I) can take place using known synthetic methods.The synthesis of the compounds of the invention, for example, can beperformed as follows: either a) by reductive amination of a substitutedbenzene compound of formula (II):

with an amine of formula (III) and subsequent splitting off of theprotective group;

wherein the R groups in formula (II) and (III) have the followingsignificance:

Ra represents a protective group, such as described, for example, in thechapter “Protective Groups in Organic Synthesis”, Chapter 7, WileyInterscience, 1991;

Rb represents NR1Ra or NR1R2, while

X, R1, R2, R5, R6, R7, R9 and R10 have the same significance as informula (I); or

b) by substitution of a substituted benzene compound of formula (IV)

 with an amine of formula HNR1R2, reduction of the nitrile group,alkylation of the amino group with a compound of formula (V) andsubsequent reduction of the nitrile group;

 wherein in formula (IV) and (V) X represents a halogen atom and R1, R2,R5, R6 and R9 have the same significance as in formula (I).

The substituted 2,5-diamino-1-aminomethylbenzene compounds of formula(I) are soluble in water and provide colors with higher color intensityor depth and outstanding color fastness, especially light fastness, washfastness and rubbing fastness.

The subject matter of the present invention also includes oxidation dyeprecursor compositions for oxidative dyeing of keratin fibers, whichnecessarily contain at least one of the substituted2,5-diamino-1-aminomethylbenzene compounds of formula 1.

These oxidation dye precursor compositions according to the inventioncontain about 0.005 to 20, preferably from 0.01 to 10, percent by weightof the substituted 2,5-diamino-1-aminomethylbenzene compound of formulaI. A content of from 0.10 to 8 percent by weight of the substituted2,5-diamino-1-aminomethylbenzene compound of formula (I) is especiallypreferred.

The compounds of formula (I) dye keratinic material in intense bluecolor shades when other dyestuffs are not present. To obtain other colorshades additional oxidation dyestuffs, for example developer substancesor coupler substances, can be used alone or in mixture with each other,together with at least one compound of formula (I).

Preferred coupler compounds for use with the compounds of formula (I) inthe compositions according to the invention include 2,6-diaminopyridine,2-amino-4-[(2-hydroxyethyl)amino]-anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxypyridine,3-amino-6-methoxy-2-(methylamino)pyridine,2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane,di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxybenzene,2,6-bis-(2-hydroxyethyl)amino-toluene, 4-hydroxyindole,3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol,5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol,5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol,3-amino-2-chloro-6-methylphenol, 3-aminophenol,2-[(3-hydroxyphenyl)amino]acetamide,5-[(2-hydroxyethyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]phenol, 3-[(2-methoxyethyl)amino]-phenol,5-amino-2-ethylphenol, 2-(4-amino-2-hydroxy-phenoxy)ethanol,5-[(3-hydroxy-propyl)amino]-2-methylphenol,3-[(2,3-dihydroxypropyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,5-amino-4-chloro-2-methylphenol, 1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methyl-benzene,3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxole,6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole and 2,3-indolindione.

Preferred developer compounds for use with the compounds of formula (I)in the compositions of the invention include 1,4-diaminobenzene;1,4-diamino-2-methylbenzene; 1,4-diamino-2,6-dimethylbenzene;2,5-diamino-1,3-diethylbenzene dihydrochloride;1,4-diamino-2,5-dimethylbenzene; 1,4-diamino-2,3-dimethylbenzene;2-chloro-1,4-diamino-benzene; 1,4-diamino-2-(thiophen-2-yl)benzenedihydrochloride; 1,4-diamino-2-(thiophen-3-yl)benzene dihydrochloride;3-(2,5-diaminophenyl)pyridine trihydrochloride; 2,5-diamino-biphenyldihydrochloride; 1,4-diamino-2-(methoxy-methyl)benzene dihydrochloride;1-(aminomethyl)-2,5-diaminobenzene-dihydrochloride;1,4-diamino-2-(hydroxymethyl)benzene;1,4-diamino-2-(2-hydroxyethoxy)-benzene dihydrochloride;2-(2-(acetylamino)ethoxy)-1,4-diamino-benzene dihydrochloride;4-phenylaminoaniline; 4-dimethylaminoaniline; 4-(dipropylamino)aniline;4-diethylaminoaniline; 4-(ethyl(2-hydroxyethyl)amino)-aniline;4-(di(2-hydroxyethyl)amino)-aniline;4-(di(2-hydroxyethyl)amino)-2-methylaniline;4-((2-methoxyethyl)amino)-aniline; 4-((3-hydroxypropyl)amino)-aniline;4-((2,3-dihydroxypropyl)amino)aniline;1,4-diamino-2-(2-hydroxyethyl)-benzene;1,4-diamino-2-(1-methylethyl)benzene;1,3-bis-((4-aminophenyl)-(2-hydroxyethyl)amino)-2-propanol;1,4-di((4-aminophenyl)amino)butane;1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane; 4-aminophenol;4-amino-3-methylphenol; 4-amino-3-(hydroxymethyl)phenol;4-amino-3-fluorophenol; 4-methylaminophenol;4-amino-2-(aminomethyl)-phenol; 4-amino-2-(hydroxymethyl)phenol;4-amino-2-fluorophenol; 4-amino-2-((2-hydroxyethyl)amino)-methylphenol;4-amino-2-methylphenol; 4-amino-2-(methoxymethyl)phenol;4-amino-2-(2-hydroxyethyl)-phenol; 5-aminosalicylic acid;2,5-diaminopyridine; 2,4,5,6-tetraaminopyrimidine;2,5,6-triamino-4(1H)-pyrimidone; 4,5-diaminobenzene;1-(2-hydroxyethyl)-1H-pyrazole;4,5-diamino-1-(1-methylethyl)-1H-pyrazole;4,5-diamino-1-((4-methylphenyl)methyl)-1H-pyrazole;1-((4-chlorophenyl)methyl)-4,5-diamino-1H-pyrazole and4,5-diamino-1-methyl-1H-pyrazole.

The oxidation dye precursor compositions according to the invention canalso contain additional dye compounds, for example 2-aminophenol,2-amino-6-methylphenol and 2-amino-5-methylphenol, as well as otherdirect-dyeing dye compounds, such as triphenylmethane dye compounds, forexample4-[(4′-aminophenyl)-(4′-imino-2″,5″-cyclohexadien-1″-yliden)-methyl]-2-methyl-aminobenzenemonohydrochloride (C.I. 42 510) and4-[(4′-amino-3′-methyl-phenyl)-(4″-imino-3″-methyl-2″,5″-cyclohexadien-1″-yliden)-methyl]-2-methyl-aminobenzenemonohydrochloride (C.I. 42 520); aromatic nitro dye compounds, such as4-(2′-hydroxyethyl)amino-nitrotoluene, 2-amino-4,6-dinitrophenol,2-amino-5-(2′-hydroxyethyl)amino-nitrobenzene,2-chloro-6-(ethyl-amino)-4-nitrophenol,4-chloro-N-(2-hydroxyethyl)-2-nitroaniline,5-chloro-2-hydroxy-4-nitroaniline, 2-amino-4-chloro-6-nitrophenol and1-[(2′-ureidoethyl)-amino-4-nitrobenzene; azo dye compounds, for example6-[(4′-aminophenyl)-azo]-5-hydroxy-naphthalene-1-sulfonic acid sodiumsalt (C.I. 14 805) and dispersion dye compounds, such as1,4-diaminoanthraquinone and 1,4,5,8-tetra-aminoanthraquinone. Thecompositions according to the invention can contain these additional dyecompounds in amounts of about 0.1 to 4.0 percent by weight. For example,it is possible to obtain blond to brown hair colors using a combinationof the compounds of formula (I) with 2-aminophenol,2-amino-6-methylphenol or 2-amino-5-methylphenol.

Understandably the coupler compounds and developer compounds as well asthe other dye compounds, in so far as they are bases, may be used in theform of their physiologically compatible salts with organic or inorganicacids, such as hydrochloric or sulfuric acid. In so far as they havearomatic OH groups they may be used in the form of salts with bases, forexample as alkali metal phenolates.

Furthermore in the case of oxidation hair dye precursor compositions,used for dyeing hair, still other conventional cosmetic additives may beincluded in the compositions. These conventional cosmetic additiveingredients include, for example, antioxidants such as ascorbic acid,thioglycolic acid or sodium sulfite, as well as perfume oils, complexformers, wetting agents, emulsifiers, thickeners and care materials. Theform of these preparations containing the dyeing agents according to theinvention can, for example, be a solution, especially an aqueous oraqueous-alcoholic solution. However the forms of the preparationaccording to the invention that are particularly preferred include acream, a gel and an emulsion. These preparations comprise a mixture ofthe dye compounds according to the invention together with theconventional cosmetic additive suitable for these preparations.

Conventional additive ingredients for the solutions, creams, emulsionsor gels include, for example, solvents, such as water, lower aliphaticalcohols, such as ethanol, propanol or isopropanol, glycerol or glycols,such as 1,2-propylene glycol; wetting agents or emulsifiers from theclasses of anionic surfactants, cationic surfactants, amphotericsurfactants and nonionic surfactants, such as fatty alcohol sulfates,ethoxylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzenesulfonates, alkyltrimethyl ammonium salts, alkylbetaines, ethoxylatedfatty alcohols, ethoxylated nonylphenols, fatty acid alkanol amides andethoxylated fatty acid esters; thickeners, such as higher fattyalcohols, starches, cellulose derivatives, petrolatum, paraffin oils andfatty acids; as well as care materials, such as cationic resins, lanolinderivative compounds, cholesterol, pantothenic acid and betaine. Theabove-mentioned additive ingredients are used in amounts suitable fortheir purposes, for example the wetting agents and emulsifiers inconcentrations of about 0.5 to 30 percent by weight, the thickeners inan amount of about 0.1 to 25% by weight and the care materials in aconcentration of about 0.1 to 5.0 percent by weight.

The oxidation dye precursor compositions according to the invention canreact weakly acidic, neutral or alkaline according to their composition.They can especially have a pH of 6.0 to 11.5, preferably adjusted withammonia. The pH however can be adjusted with organic amines, for examplemonoethanolamine and triethanolamine, or inorganic bases, such as sodiumhydroxide and potassium hydroxide. Inorganic or organic acids, forexample phosphoric acid, acetic acid, citric acid or tartaric acid, canbe used for adjustment of pH in the acid range.

In order to use the oxidation dye precursor composition according to theinvention for dyeing hair immediately prior to application to the hair asufficient amount of this dye precursor composition for dyeing the hair,generally about 60 to 200 g, is mixed with an oxidizing agent. Then theresulting ready-to-apply dye mixture is applied to the hair.

Primarily hydrogen peroxide, or its addition compound with urea,melamine, sodium borate or sodium carbonate, is used as oxidizing agentto develop the hair colors, in the form of a 3- to 12-percent,preferably 6-percent, aqueous solution, however air oxygen can also beconsidered. If a 6-percent hydrogen peroxide solution is used asoxidizing agent, the weight ratio of oxidation dye precursor compositionand oxidizing agent is 5:1 to 1:2, preferably however 1:1. Largeramounts of oxidizing agent are above all used with higher dye compoundconcentrations in the oxidation dye precursor composition, or if a amore intense bleaching or lightening of the hair color is intended atthe same time. The ready-to-apply dye mixture is allowed to act on thehair for about 10 to 45 minutes, preferably 30 minutes, at 15 to 50° C.,after being applied to the hair. Then the dye mixture is rinsed from thehair with water and the hair is dried. If necessary the hair may bewashed with a shampoo in connection with the rinsing and after-rinsedwith a weak organic acid, for example citric or tartaric acid, asneeded. Finally the hair is dried.

The oxidation dye precursor compositions containing the substituted2,5-diamino-1-aminomethylbenzene compounds of formula (I) provide dyedhair colors having outstanding color fastness, especially lightfastness, wash fastness, and fastness to rubbing. They provide a broadpalette of various color shades and tones, which extend from blondshades to brown, purple, violet up to blue and black color shadesaccording to the type and amounts of their various dye compoundingredients. The very good dyeing properties of the dye precursorcompositions according to the invention are characterized by the factthat they can dye gray, chemically undamaged hair without difficultiesand with good color coverage or color depth. The compounds of formula Ialso can be employed to produce intense blue colors on keratin fiberswithout addition of other dye compounds.

The following examples should illustrate the subject matter of thepresent invention in detail, without limiting the broad concept of theinvention or the claims appended hereinbelow.

EXAMPLES Process Examples Example 1 Synthesis of Substitued2,5-diamino-1-aminomethylbenzene Compounds of Formula (I) (GeneralSynthetic Recipe)

A. Synthesis of 2,5-bis-tert.-butyloxycarbonylaminobromobenzene

15.65 g (0.07 mol) bromo-p-phenylenediamine hydrochloride and 32.7 g(0.15 mol) di-tert-butyl dicarbonate are dissolved in a mixture of 250ml 2N sodium hydroxide solution and 250 ml trifluorotoluene and themixture is heated at 45° C. The reaction mixture is stirred for 3 days.Additional 30 g (0.14 mol) di-tert.-butyl dicarbonate are addedgradually.

Subsequently the organic layer is separated and the aqueous phase isextracted twice with 100 ml of dichloromethane. The combined extractsare evaporated to form a residue and the residue is taken up in 200 mlof hexane. The precipitate is separated by filtration and washed with 50ml hexane. 18.6 g (82% of theoretical) of2,5-bis-tert.-butyloxycarbonylaminobromobenzene were obtained with amelting point of 130° C.

B. Synthesis of N-(4-tert.-butyloxycarbonylamino-2-formylphenyl)carbamicacid-tert.butyl ester

3.3 g (0.01 mol) 2,5-bis-tert.-butyloxycarbonylamino-bromobenzene fromstep A are dissolved in 100 ml of water-free tetrahydrofuran underargon. Gradually 17 ml of a 1.6 molar methyl lithium ether solution(0.03 mol) are added. The reaction mixture is cooled to −20° C.Subsequently 7 ml of 1.5 molar t-butyl lithium solution (0.01 mol) areadded gradually. After ending the addition the solution is stirred for30 minutes at −20° C. Subsequently 1.2 g of dimethylformamide (0.02 mol)are added and the reaction mixture is stirred for an hour at −20° C.After slow heating to room temperature the reaction mixture ishydrolyzed with water and then poured into ether, the aqueous phase isextracted with ether and then the organic phase is dried with magnesiumsulfate. The solvent is distilled off in a rotary evaporator and theresidue is purified on silica gel with petroleum ether/ethyl acetate(9:1).

C. Synthesis of the Substituted 2.5-diamino-1-aminomethylbenzenes

0.033 9 (0.0001 mol) ofN-(4-tert.-butyloxycarbonylamino-2-formylphenyl)carbamic acid-tert.butylester from step B and 0.00015 mol of a suitable amine are dissolved in1,2-dichloroethane. Subsequently 0.1 mol of an acetic acid solution (1m, in 1,2-dichloroethane) and 0.06 g NaBH(OAc)₃ (0.0003 mol) are addedand the resulting reaction mixture is stirred for 5 to 15 hours. Afterthe reaction has ended the reaction mixture is poured into 10 ml ofethyl acetate, the organic phase is extracted with sodium hydrogencarbonate and then dried with magnesium sulfate. The solvent isdistilled off in a rotary evaporator and the residue is purifiedchromatographically with petroleum ether/ethyl acetate (9:1). Theproduct obtained is heated in 4 ml of ethanol at 50° C. Subsequently 1.5ml of 2.9 molar ethanolic hydrochloric acid solution are added dropwiseto make the hydrochloride. The precipitate is filtered, washed twicewith ethanol and then dried.

a. 4-(2,5-diaminobenzylamino)aniline hydrochloride

Amine used: 4-tert.-butyloxycarbonylamino-aniline

Yield: 0.025 g (67% of theory)

Mass spectrum: MH⁺ 229 (100)

b. 2-(4-amino-2-methylphenyl)aminomethyl-1,4-diaminobenzenehydrochloride and 2-(4-amino-3-methylphenyl)aminomethyl-14-diaminobenzene; hydrochloride

Amine used: 4-tert.butyloxycarbonylamino-3-methylaniline and4-tert.-butyloxycarbonylamino-2-methylaniline

Yield: 0.025 g (27% of theory)

Mass spectrum: MH⁺ 243 (80)

c. 2-(3-aminophenyl)aminomethyl-1,4-diaminobenzene hydrochloride

Amine used: 3-tert.-butyloxycarbonylamino-aniline

Yield: 0.025 g (67% of theory)

Mass spectrum: MH⁺ 229 (100)

d. 2-[5-amino-2-(2,5-diaminobenzylamino)phenyl]ethanol hydrochloride and2-[2-amino-5-(2,5-diaminobenzylamino)phenyl]ethanol hydrochloride

Amine used: 4-tert.-butyloxycarbonylamino-3-(2-hydroxyethyl)aniline and4-tert.-butyloxycarbonylamino-2-(2-hydroxyethyl)aniline

Yield: 0.025 g (30% of theory)

Mass spectrum: MH⁺ 273 (100)

e. 2-[4-amino-2-(2,5-diaminobenzylamino)phenoxy]ethanol hydrochloride

Amine used:4-tert.butyloxycarbonylamino-2-amino-(2-hydroxy)-ethoxybenzene

Yield: 0.025 g (58% of theory)

Mass spectrum: MH⁺ 289 (100)

f. 2-(4-dimethylaminophenyl)aminomethyl-1,4-diaminobenzene hydrochloride

Amine used: 4-amino-N,N-dimethylaniline

Yield: 0.025 g (62% of theory)

Mass spectrum: MH⁺ 257 (100)

TABLE I ABBREVIATIONS USED IN EXAMPLES 3 TO 17 Substituted2,5-diamino-1-aminomethylbenzene(s) of Formula (I) E1a4-(2,5-diaminobenzylamino)aniline hydrochloride E1b2-(4-amino-2-methylphenyl)aminomethyl-1,4-diamino- benzenehydrochloride/2-(4-amino-3-methylphenyl)amino- methyl-1,4-diaminobenzenehydrochloride E1c 2-(3-aminophenyl)aminomethyl-1,4-diaminobenzeneHydrochloride E1d 2-[5-amino-2-(2,5-diaminobenzylamino)phenyl]ethanolhydrochloride/2-[2-amino-5-(2,5-diaminobenzyl- amino)phenyl]ethanolhydrochloride E1e 2-[4-amino-2-(2,5-diaminobenzylamino)phenoxy]ethanolhydrochloride E1f2-(4-dimethylaminophenyl)aminomethyl-1,4-diaminobenzene hydrochlorideDeveloper Substances E2 1,4-diaminobenzene E3 2,5-diaminophenylethanolsulfate E4 2,5-diaminotoluene sulfate Coupler Substances K131,3-diamino-4-(2′-hydroxyethoxy)benzene sulfate K225-amino-2-methylphenol K25 1-naphthol K31 1,3-dihydroxybenzene DyestuffD1 2-amino-5-methylphenol D2 2-amino-6-methylphenol D52-amino-6-chloro-4-nitrophenol

Examples 3 to 11 Hair Dye Precursor Compositions

HAIR DYE SOLUTIONS: X g 4-(2,5-diaminobenzylamino)aniline hydrochloride(E1a) U g developer substance E1 to E9 according to the following TableII Z g dyestuff D according to the following table II 10.0 g potassiumoleate (8 percent aqueous solution) 10.0 g ammonia (22 percent aqueoussolution) 10.0 g ethanol 0.3 g ascorbic acid to 100.0 g water

30 g of the above-described hair dye solution are mixed with 30 g of a 6percent hydrogen peroxide solution immediately prior to application.Subsequently the mixture is applied to bleached hair. After an actingtime of 30 minutes at 40° C. the hair is rinsed with water, washed witha commercial shampoo and dried. The resulting dyed hair colors aretabulated in the following Table II.

TABLE II COMPOSITIONS OF EXAMPLES 3 TO 11 AND DYED HAIR COLORS PRODUCEDUSING EXAMPLES 3 TO 11* Example No./ Dyestuff 3 4 5 6 7 8 9 10 11 E1a0.90 0.37 0.30 0.38 0.38 0.38 0.38 0.38 0.30 E2 0.12 E3 0.15 E9 0.13 D10.18 0.18 0.18 0.18 0.06 0.18 0.30 D2 0.18 0.24 D5 0.12 Color DeepMedium Medium Black- Brown Black- Medium Brown Red- Blue Brown BlondBrown Brown Brown brown *Amounts of the dyestuffs are listed in grams.

Examples 12 to 17 Hair Dye Precursor Compositions

HAIR DYE SOLUTIONS: 0.00125 mol substituted2,5-diamino-1-amionmethylbenzene compound of formula I according to thefollowing Table III (E1a to E1f) 0.00125 mol coupler substance Kaccording to Table III 1.0 g potassium oleate (8 percent aqueoussolution) 1.0 g ammonia (22 percent aqueous solution) 1.0 g ethanol 0.3g ascorbic acid to 100.0 g water

30 g of the above-described hair dye solution are mixed with 30 g of a 6percent hydrogen peroxide solution immediately prior to application.Subsequently the mixture is applied to bleached hair. After an actingtime of 30 minutes at 40° C. the hair is rinsed with water, washed witha commercial shampoo and dried. The resulting dyed hair colors aretabulated in the following Table III.

TABLE III DYED HAIR COLORS PRODUCED USING EXEMPLARY HAIR DYE SOLUTIONS12 TO 17 Coupler/ Example Developer K31 K13 K22 K25 12 E1a Blue Deepblue Blue Deep blue 13 E1b Violet Deep blue Violet Blue 14 E1c Deep blueDeep blue Gray-rose Grey-blue 15 E1d Violet Deep blue Violet Violet 16E1e Gray-blue Gray-blue Gray-blue Grey-blue 17 E1f Bright Ash Grey-bluePurple Gray-rose Blond

Example 18 Oxidation Hair Dye Precursor Composition

0.32 g 2,5-diaminotoluene hydrochloride 0.04 g 5-amino-2-methylphenol0.09 g 4-(2,5-diaminobenzylamino)aniline hydrochloride 0.03 g3-aminophenol 0.03 g 1,3-dihydroxybenzene 0.04 g1,3-dihydroxy-2-methylbenzene 0.10 g 4-amino-3-methylphenol 0.20 g2-amino-5-methylphenol 0.10 g 2-amino-6-methylphenol hydrochloride 0.01g 4-chloro-N-(2-hydroxyethyl)-2-nitroaniline 0.02 g2-amino-4,6-dinitrophenol 0.10 g 2-chloro-6-(ethylamino)-4-nitrophenol10.00 g potassium oleate (8 percent aqueous solution) 10.00 g ammonia(22 percent aqueous solution) 10.00 g ethanol 0.30 g ascorbic acid to100.0 g water

30 g of the above-described hair dye solution are mixed with 30 g of a 6percent hydrogen peroxide solution immediately prior to application.Subsequently the mixture is applied to bleached hair. After an actingtime of 30 minutes at 40° C. the hair is rinsed with water, washed witha commercial shampoo and dried. The resulting dyed hair color was brown.

Example 19 Oxidation Hair Dye Precursor Composition

0.32 g 2,5-diaminophenylethanol sulfate 0.04 g 5-amino-2-methylphenol0.05 g 4-(2,5-diaminobenzylamino)aniline hydrochloride 0.03 g3-aminophenol 0.03 g 1,3-dihydroxybenzene 0.04 g1,3-dihydroxy-2-methylbenzene 0.10 g 4-amino-3-methylphenol 0.20 g2-amino-5-methylphenol 0.10 g 2-amino-6-methylphenol hydrochloride 0.01g 4-chloro-N-(2-hydroxyethyl)-2-nitroaniline 0.02 g2-amino-4,6-dinitrophenol 0.10 g 2-chloro-6-(ethylamino)-4-nitrophenol10.00 g potassium oleate (8 percent aqueous solution) 10.00 g ammonia(22 percent aqueous solution) 10.00 g ethanol 0.30 g ascorbic acid to100.0 g water

30 g of the above-described hair dye solution are mixed with 30 g of a 6percent hydrogen peroxide solution immediately prior to application.Subsequently the mixture is applied to bleached hair. After an actingtime of 30 minutes at 40° C. the hair is rinsed with water, washed witha commercial shampoo and dried. The resulting dyed hair color was brown.

All percentages given herein are percentages by weight, unless otherwiseindicated.

The disclosure in German Patent Application 199 61 274.9 of Dec. 18,1999 is incorporated here by reference. This German Patent Applicationdescribes the invention described hereinabove and claimed in the claimsappended hereinbelow and provides the basis for a claim of priority forthe instant invention under 35 U.S.C. 119.

While the invention has been illustrated and described as embodied insubstituted 2,5-diamino-1-aminomethylbenzene compounds and oxidation dyeprecursor compositions for dyeing keratin fibers, especially human hair,containing these compounds, it is not intended to be limited to thedetails shown, since various modifications and changes may be madewithout departing in any way from the spirit of the present invention.

Without further analysis, the foregoing will so fully reveal the gist ofthe present invention that others can, by applying current knowledge,readily adapt it for various applications without omitting featuresthat, from the standpoint of prior art, fairly constitute essentialcharacteristics of the generic or specific aspects of this invention.

What is claimed is new and is set forth in the following appendedclaims.

We claim:
 1. An oxidation hair dye precursor composition containing atleast one substituted 2,5-diamino-1-aminomethylbenzene compound offormula (I), or a physiologically compatible water-soluble salt thereof,

wherein R1, R2, R3, R4, R5, R6 and R7, independently of each other, eachrepresent hydrogen, a C₁- to C₆-alkyl group, a C₁- to C₄-hydroxyalkylgroup, a C₂- to C₄-dihydroxyalkyl group or a C₁- to C₄-alkoxy-(C₁- toC₂)-alkyl group or at least one pair selected from the group consistingof R1 and R2; R3 and R4; and R5 and R6, together with the N atom form afour-member to eight-member aliphatic ring, with the proviso that atleast two of said R1 to R6 each represent said hydrogen; R8 representshydrogen, a halogen atom, a C₁- to C₄-alkyl group, a C₁- toC₄-hydroxyalkyl group or a C₁- to C₄-alkoxy group; R9 representshydrogen, a halogen atom, a cyano group, a hydroxy group, a C₁- toC₄-alkoxy group, a C₁- to C₄-hydroxyalkoxy group, a C₁- to C₆-alkylgroup, a C₁- to C₄-alkylthioether group, a mercapto group, an aminogroup, a C₁- to C₄-alkylamino group, a C₁- to C₄-hydroxyalkylaminogroup, a di(C₁- to C₄-alkyl)amino group, a di(C₁- toC₄-hydroxyalkyl)amino group, a [dihydroxy(C₂- to C₄)-alkyl]amino group,a (C₁-C₄-hydroxyalkyl)-(C₁-C₄-alkylamino group, a trifluoromethanegroup, a C₁- to C₄-hydroxyalkyl group or a C₃- to C₄-dihydroxyalkylgroup; and R10 represents hydrogen or a (C₁- to C₆-)alkyl group.
 2. Anaqueous or aqueous-alcoholic oxidation dye precursor composition fordyeing keratin fibers, said oxidation dye precursor compositioncomprising: water; at least one additive ingredient selected from thegroup consisting of aliphatic alcohols, glycerol, glycols, anionicsurfactants, cationic surfactants, nonionic surfactants, amphotericsurfactants, thickeners, care materials, antioxidants, perfume oils,complex formers and pH adjusting agents; and from 0.1 to 10 percent byweight of at least one substituted 2,5-diamino-1-aminomethylbenzenecompound, or a physiologically compatible water-soluble salt thereof,wherein said at least one substituted 2,5-diamino-1-aminomethylbenzenecompound is selected from the group consisting of2-((2-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-aminophenylamino)-methyl)-1,4-diaminobenzene;2-((4-amino-phenylamino)methyl)-1,4-diaminobenzene;2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-dimethylamino-phenylamino)methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((3-aminophenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((4amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹,N¹-bis(hydroxyethyl)-2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((4-bis(2-hydroxyethyl)amino-phenylamino)methyl)-1,4-diaminobenzene;N¹-dihydroxypropyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxy-ethyl)-2-((4-bis(2-hydroxyethyl)-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴,N⁴-bis(hydroxyethyl)-2-((4-dimethylamino-phenyl-amino)-methyl)-1,4-diamino-benzene;N⁴-dihydroxypropyl-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;N⁴-dihydroxypropyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diamino-benzene;2-((2-(2-hydroxyethyl)aminophenyl-amino)-methyl)-1,4-diamino-benzene;2-((2-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-dihydroxypropylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(2-hydroxyethyl)-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-dihydroxypropylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-dihydroxypropylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-methylamino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(2-hydroxyethyl)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-(2-hydroxyethyl)-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-chloro-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-chloro-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methoxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methoxy-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methyl-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((2-methyl-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(2-hydroxyethyl)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-(2-hydroxyethyl)-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-chloro-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-chloro-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methoxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methoxy-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene2-((3-methyl-4-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((3-methyl-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethoxy)-3-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene;2-((4-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzeneand2-((4-(2-hydroxyethyl)-3-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene.3. The aqueous or aqueous-alcoholic oxidation dye precursor compositionas defined in claim 2, further comprising at least one coupler compoundselected from the group consisting of 2,6-diaminopyridine,2-amino-4-[(2-hydroxyethyl)amino]-anisole,2,4-diamino-1-fluoro-5-methyl-benzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxy-pyridine,3-amino-6-methoxy-2-(methylamino)pyridine,2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)-amino]aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,3-[(2-aminoethyl)-amino]aniline, 1,3-di(2,4-diaminobenzene;phenoxy)propane, di(2,4-diaminophenoxy)-methane,1,3-diamino-2,4-dimethoxybenzene, 2,6-bis-(2-hydroxyethyl)amino-toluene,4-hydroxyindole, 3-dimethylaminophenol, 3-diethylaminophenol,5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol,5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol,3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol,3-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-aminophenol,2-[(3-hydroxyphenyl)amino]acetamide,5-[(2-hydroxyethyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]phenol, 3-[(2-methoxyethyl)amino]-phenol,5-amino-2-ethylphenol, 2-(4-amino-2-hydroxy-phenoxy)ethanol,5-[(3-hydroxypropyl)amino]-2-methylphenol,3-[(2,3-dihydroxypropyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,5-amino-4-chloro-2-methylphenol, 1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methyl-benzene,3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxole,6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole and 2,3-indolindione.
 4. The aqueous oraqueous-alcoholic oxidation dye precursor composition as defined inclaim 2, further comprising at least one developer substance selectedfrom the group consisting of 1,4-diaminobenzene;1,4-diamino-2-methylbenzene; 1,4-diamino-2,6-dimethylbenzene;2,5-diamino-1,3-diethylbenzene dihydrochloride;1,4-diamino-2,5-dimethylbenzene; 1,4-diamino-2,3-dimethylbenzene;2-chloro-1,4-diamino-benzene; 1,4-diamino-2-(thiophen-2-yl)benzenedihydrochloride; 1,4-diamino-2-(thiophen-3-yl)benzene dihydrochloride;3-(2,5-diaminophenyl)pyridine trihydrochloride; 2,5-diamino-biphenyldihydrochloride; 1,4-diamino-2-(methoxy-methyl)benzene dihydrochloride;1-(aminomethyl)-2,5-diaminobenzene-dihydrochloride;1,4-diamino-2-(hydroxymethyl)benzene;1,4-diamino-2-(2-hydroxyethoxy)-benzene dihydrochloride;2-(2-(acetylamino)ethoxy)-1,4-diamino-benzene dihydrochloride;4-phenylaminoaniline; 4-dimethylaminoaniline; 4-(dipropylamino)aniline;4-diethylaminoaniline; 4-(ethyl(2-hydroxyethyl)amino)-aniline;4-(di(2-hydroxyethyl)amino)-aniline;4-(di(2-hydroxyethyl)amino)-2-methylaniline;4-((2-methoxyethyl)amino)-aniline; 4-((3-hydroxypropyl)amino)-aniline;4-((2,3-dihydroxypropyl)amino)aniline;1,4-diamino-2-(2-hydroxyethyl)-benzene;1,4-diamino-2-(1-methylethyl)benzene;1,3-bis-((4-aminophenyl)-(2-hydroxyethyl)amino)-2-propanol;1,4-di((4-aminophenyl)amino)butane;1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane; 4-aminophenol;4-amino-3-methylphenol; 4-amino-3-(hydroxymethyl)phenol;4-amino-3-fluorophenol; 4-methylaminophenol;4-amino-2-(aminomethyl)-phenol; 4-amino-2-(hydroxymethyl)phenol;4-amino-2-fluorophenol; 4-amino-2-((2-hydroxyethyl)amino)-methylphenol;4-amino-2-methylphenol; 4-amino-2-(methoxymethyl)phenol;4-amino-2-(2-hydroxyethyl)-phenol; 5-aminosalicylic acid;2,5-diaminopyridine; 2,4,5,6-tetraaminopyrimidine;2,5,6-triamino-4(1H)-pyrimidone;4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole;4,5-diamino-1-(1-methylethyl)-1H-pyrazole;4,5-diamino-1-((4-methylphenyl)methyl)-1H-pyrazole;1-((4-chlorophenyl)methyl)-4,5-diamino-1H-pyrazole and4,5-diamino-1-methyl-1H-pyrazole.
 5. The aqueous or aqueous-alcoholicoxidation dye precursor composition as defined in claim 2, wherein saidkeratin fibers are human hair and further comprising at least oneadditional dyestuff selected from the group consisting of 2-aminophenol,2-amino-6-methylphenol, 2-amino-5-methylphenol, triphenylmethylene dyecompounds, aromatic nitro dye compounds, azo dye compounds anddispersion dye compounds.
 6. A method of dyeing hair, said methodcomprising the steps of: a) mixing an oxidation dye precursorcomposition with an oxidizing agent in a weight ratio of 5:1 to 1:2 toform a ready-to-apply hair dyeing mixture, said oxidation dye precursorcomposition comprising at least one substituted2,5-diamino-1-aminomethylbenzene compound of formula (I), or aphysiologically compatible water-soluble salt thereof,

 wherein R1, R2, R3, R4, R5, R6 and R7, independently of each other,each represent hydrogen, a C₁- to C₆-alkyl group, a C₁- toC₄-hydroxyalkyl group, a C₂- to C₄-dihydroxyalkyl group or a C₁- toC₄-alkoxy-(C₁- to C₂-)alkyl group or at least one pair selected from thegroup consisting of R1 and R2; R3 and R4; and R5 and R6 together withthe N atom form a four-member to eight-member aliphatic ring, with theproviso that at least two of said R1 to R6 each represent said hydrogen;R8 represents hydrogen, a halogen atom, a C₁- to C₄-alkyl group, a C₁-to C₄-hydroxyalkyl group or a C₁- to C₄-alkoxy group; R9 representshydrogen, a halogen atom, a cyano group, a hydroxy group, a C₁- toC₄-alkoxy group, a C₁- to C₄-hydroxyalkoxy group, a C₁- to C₆-alkylgroup, a C₁- to C₄-alkylthioether group, a mercapto group, an aminogroup, a C₁- to C₄-alkylamino group, a C₁- to C₄-hydroxyalkylaminogroup, a di(C₁- to C₄-alkyl)amino group, a di(C₁- toC₄-hydroxyalkyl)amino group, a {dihydroxy(C₂- to C₄)-alkyl}amino group,a (C₁- to C₄-hydroxyalkyl)-C₁-C₄-alkylamino group, a trifluoromethanegroup, a C₁-C₄-hydroxyalkyl group or a C₃-C₄ dihydroxyalkyl group; andR10 represents hydrogen or a C₁- to C₆-alkyl group; b) applying asufficient amount of the ready-to-apply hair dyeing mixture to hair inorder to dye the hair; c) after the applying of step b), allowing theready-to-apply hair dyeing mixture to act on the hair for 10 to 45minutes at 15 to 50° C.; d) after the allowing of step c), rinsing thehair with water and washing the hair with a shampoo as needed; and e)subsequently drying the hair.
 7. The method as defined in claim 6,wherein said oxidizing agent is hydrogen peroxide or an additioncompound of hydrogen peroxide with urea, melamine, sodium borate orsodium carbonate.
 8. The oxidation hair dye precursor composition asdefined in claim 1, containing from 0.005 to 20 percent by weight ofsaid at least one substituted 2,5-diamino-1-aminomethylbenzene compoundof the formula (I), or said physiologically compatible water-solublesalt thereof.
 9. The oxidation hair dye precursor composition as definedin claim 1, further comprising at least one additional dyestuff selectedfrom the group consisting of developer substances, coupler substances,2-aminophenol, 2-amino-6-methylphenol and direct-dyeing dye compounds.